Cupriferous polyazo dyestuffs



Patented July 7, 1 953 Hans Ruckstuhl and Walter Wehrli, Basel, Switzerland, assignors to Sandoz A. G., Basel, Switzerland, a Swiss firm No Drawing. Application December 3, 1951, Se-

rial No. 259,692. In Switzerland December 7,

' 6 Claims. (01. 260-145) The present invention relates to polyazo dyestufis.

A primary object of the invention is the embodiment of a group of polyazo dyestuifs characterized by superior aflinity for textile fibers, especially cotton and regenerated cellulose, and

by their ability to yield dyeings in light-fast and Wash-fast bluish shades. a

This object is realized, according to the present invention, by the copper complex compounds of the group of polyazo dyestuffs which correspond to the formula series-which, in ortho-position to the azo group, is substituted by a COOH, OCHa ore-H group, and which may bear further substituents, including arylazo groups, and wherein R stands for the radial of a monohydroxyor dihydroxynaphthalene-mono-, dior trisulfonic acid, coupled in ortho-position to hydroxy, or for the radical of an aminohydroxynaphthalenemonoor di-sulfonic acid, the amino group of which may be alkylated, arylated or acylated.

10 A desired copper complex compound, according to the present invention, isobtained by com- (FOE! 00133 wherein a stands for a carboxy, methoxy or hydroxy group, b stands for hydrogen,alower alkyl group, an N=N-mononuclear aryl radical or a nitro group, :1: stands for hydrogen, OH, NH:;, alkylated Nl-l2,'acylated NI-Iz orsulfo, 1/ stands bining the diazo compound of an appropriate amine of the formula ANlh I with an appropriate azo dyestuif of the formula for an OH group in ortho-position to azo-, 0H

one 12 is the integer 2 and the other as are the integers 1 or 2, and which contain at least 3 atoms of copper to the molecule. t

These copper complex compoundsfin'ayalso be defined as cupriferous derivatives of polyazodyestuffs which correspond to the formula wherein one A is an i OCH:

N=NA or with the copper complex compound of the latter, or by combining the diazo compound of 40 the amine of the formula V Hols OH 7 group and the other A is a radical of the benzene or with the copper complex compound of the etc.

latter, A having in each case the previously-indicated significance, and. then subjecting the resultant polyazo dyestuff to a demethylating coppering.

Illustrative R radicals are the radicals of, for example:

l-hydroxynaphthalene-4-sulfonic acid, 2-hydroxynaphthalene-4-sulfonic acid, 2-hydroxynaphthalene-fi-sulfonic acid, 1-hydroxynaphthalene-3,fi-disulfonic acid, 2-hydroxynaphtha1ene-3,6-disu1fonic acid, 1-hydroxynaphthalene-3,8-disulfonic acid, 1-hydroxynaphthalene-3,6,8-trisulfonic acid, 2 acetylamino 5 hydroxynaphthalene '7- sulfonic acid,

2 benzoylamino 5 hydroxynaphthalene 7- sulfonic acid,

2 methylamino 5 hydroxynaphthalene '7- sulfonic acid, 7

2 phenylamino 5 hydroxynaphthalene '7- sulfonic acid,

1 phenylamino 8 hydroxynaphthalene 4-- sulfonic acid,

2 phenylamino 8 hydroxynaphthalene 6- sulfonic acid,

1 acetylamino 8 hydroxynaphthalene 3,6-

disulfonic acid,

1 benzoylamino 8 hydroxynaphthalene 4,6-

disulfonic acid,

2 acetylamino 8 hydroxynaphthalene 3,6-

disulfonic acid,

1,8 dihydroxynaphthalene acid, etc.

Illustrative A aryl radicals which, in orthoposition to the azo group, are substituted by a COOH, -OCH3 or --OH group, are the rad1- cals of, for example:

2-amino-l-hydroxy-benzene-4-sulfonic acid, 2-amino-l-hydroxy-benzene-5-sulfonic acid, 2-amino-1-methoxybenzene, 2-amino-1-methoxy-4-methylbenzene, 2-amino-1-methoxy-5-chlorobenzene, 2-amino-1-methoxy-5-nitr0benzene, Z-amino-l-methoxybenzene-4-sulfonic acid, 2-amino-l-methoxy 5 nitrobenzene-4-sulfon1c acid, 2-amino 1 methoxy 5 chlorobenzene-4-sulionic acid,

3,6 disulfonic 2-aminobenzene 1-carboxylic acid,

2-amino-5-nitrobenzene-l-carboxylic acid, 2-amino-5-chlorobenzene-l-carboxylic acid,

:Z-amino-1ecarboxybenzene-4-sulfonic acid,

2-amino-1-carboxybenzene-5-sulfonic acid,

4 amino 4' hydroxy-Ll-azobenzene-3,3'-dicarboxylic acid,

4 amino-4'-hydroxy 3 methoxy-1,l-azobenzene-3'-carboxylic acid, etc;

also monoazo dyestuffs prepared by coupling diazotized aminobenzene-monosulfonic acids or -d1- isulfonic acids or diazotized aminonaphthalene- :mcnosulfonic acids or -disulfonic acids with lamino-2-methoxybenzene or substitution products thereof which are capable of coupling, for instance the following dyestuffs:

l amiriobenzene-4 sulfonic acid l-methoxy-Z-amino-4-methylbenzene, 1-aminobenzene-2,5-disulfonic acid 1-methoxy-2 -aminoe lemethylbenzene, l-aminonaphthalene4-sulfonic acid 1-methoxy-2-amino-l-methylbenzene, 2-aminonaphthalene-4,8-disulfonic acidl-methoxy-2amino-4-methylbenzene,

HOzB OH OH Y N=N BOzH are preferably prepared by acid coupling of a diazotised aminobenzene sulfonic acid with a 2- amino-5-acyloxy-naphthalene '7 sulfonic acid, replacement of the amino group of the naphthalene radical by a hydroxyl group, introduction of a hydroxyl group into the benzene radical by an oxidative' coppering and splitting oil theacyl radical in the acyl-oxy group of the naphthalene radical.

For further coupling, it is advantageous to em-' ploy the coupling components in the form of the copper complex compound.

The obtained polyazo dyestufis are treated with copper-yielding agents until the methoxy groups are split, and the dyestuffs are converted into the copper complexes.

Coppering of the dyestuffs can be carried out according to various methods which per se are known from the literature, for example, by heating in weakly alkaline aqueous agents with copper tetramine hydroxide complex, optionally in the presence of an organic base, or in a fusion of alkali metal salts of low-molecular aliphatic monocarboxylic acids with copper salts.

The polyazo dyestuffs obtained according to the present invention dye cotton and regenerated cellulose in marine-blue to blue-green shades. The resultant dyeings possess an outstandin'g'airlnity for the fiber and have a very good fastness to light and to washing.

The following examples set forth representative exemplary embodiments of the invention, and these examples are intended to be solely illustrative and not at all limitative. In these examples, the parts and percentages are by weight and the temperatures are expressed in degrees centigrade.

The term soda as hereinafter employed refers to sodium carbonate.

Example v1 The tetrazo compound from 24.4 parts of 3,3- dimethoxy-4,4'-diamino 1,1 diphenyl is subjected to alkaline coupling in per se conventional 3 OH coon 6 in 500'parts of water-,-500parts of pyridine and -11 1-7;: 12:1 50 parts of aqueous ammonia of strength. ;Ezample 3 Upon conclusion of the coupling, the trisazo dyestufi is isolated and subjected to demethylating ii:- I" 1 coppering in substance according to per se con- The tetrazo compound from parts or venti0na1meth0ds 5 5 dimethoxy-4,4'-diamino-1,1'-diphenyl is sub- In the dry state, the, copper complexof the dye- Jected to soda-alkaline o l i P 88 convenstuff is a dark powder which dissolves in water tional manner with 30.4 parts o y y p with a blue coloration and in concentrated sulthalene-3,8-disulfonic acid. The resultant infuric acid with blue-green coloration, and dyes l0 immediate 1 a de t5 a' solutio fi 1 45 parts of cotton in fast marine-blue'shades. It corresponds to the composition: I, I

Cu-O

Boss 0 Example 2 I I the copper compleic of the monoazo dyestufi of The tetrazo compound from 24.4 parts of 3,3 composltiom dimethoxy-4,4'-diamino-1,1'-diphenyl is "sub- 26 jected to soda-alkaline coupling in per se conventional manner with 30.4 parts of l-hydroxynaphthalene-3,8-disulfonic acid. The resultant intermediate is added to a solution of 49.5 parts of 7 v I the copper complex of the 'monoazo dyestuif of 30 the composition: I I,

, 500 parts of pyridine audio parts or aqueous H035 .()H @0011 I V i ammonia 0f'25% strength in 500 parts of water.

1 Upon-conclusion of the coupling, the tri'sa'z'o dyestufi is isloated and subjected to 'demethylating coppering in per se conventional manner 500 parts of pyridine and part of aqueous 4D with ammoniacal copper oxide in aqueous soluammonia of 25% strength in'500 parts of water. 171011 in Presence O an Organic e t Upon conclusion of the coupling, the trisaz'o dye- I In the dry Sta the pp complex 0f y stuff is isolated and subjected to demethylating stuff is a dark powder which dissolves in water coppering in per se conventional manner with with a bluecoloration and in concentrated sule ammoniacal copper oxide in aqueous solution 45 furic acid with a blue-green coloration, and dyes in presence of an organic base at 95. .1 cotton in fast marineblueshades. It corre- In the dry state, the copper complex 01" the sponds to the composition:

dyestufi is a dark powder which dissolves in wa-1, i, v fi fli t ter with a blue coloration and in concentrated ,Tht'trazocoifipound fr6m"24.4 parts of ,3- sulfuric acid with blue-green coloration, and dyes dimethoxy-4,4'-diamino-1,1rdipheny1, is sub cotton in fast marine-blue shades. It corre 'iec'ted to soda-alkaline coupling in'per se convensponds to the composition; tional manner with 30.4 parts of l-hydroxynaph- H035 I o ,Cu-O

SOaH

thalene-3,6-disultonic acid. The resultant inparts of the copper complex of'the monoazo dyetermediate is added to .9. solution of 53 parts of stuff of the composition:

the copper complex or the monoazo dyestufl or on the.conmosition:-

on 1 V a 5 B on coon vHo s j on coon 500 parts of pyridine and 50 parts-of aqueous ammonia of 25% strength in 500 parts of water.

Uponconclusion of the coupling thetrisazo dye: 500 parts of pyridine and Parts of aqueous stufi is isolateduand subjected to demethylating monia 0f strength In 500 parts of water- P coppering with copperisulfateina-sodium acetate Upon conclusion of the coupling, the trisazo dyefusion stutI is isolated and subjected to demethylating V In the dry state, the copper complex of th dyepp l Wlth copper Sulfate in a Sodlum -stuff is a dark powder which dissolves in water tate fus1on. i with blue coloration and in concentrated sulfuric In the y State. the 1 9 93 1 of the acid with blue-green coloration, and dyes cotton dyestufi 1s a dark powder Whlch dlSSOll/GS in in fast blue-green shades. It corresponds to the ter with a blue coloration and in concentrated composition;

nos 0 ouo O-Cu H038 -so,n I 110,

sulfuric acid with blue-green coloration, and dyes E 6 cotton in fast marine-b1ue shades. It corresample sponds to the composition: The tetrazo compound from 24.4 parts of 3,3-

0 Cu0 O-Cu 0 i l l N=$T V l=N I om H0 o-ou c=o i A marine-blue dyestuff with similar properties dimethoxy 4.4'-diamlno-1,1'-dipheny1 is sub is obtained in entirely analogous manner when jected to alkaline coupling in per se conventional theprecedingly-mentioned intermediate is coumanner with 38.4 parts of l-hydroxynaphthapied with the. copper complex of the monoazo lene-3,6,8-trisulfonic acid The resultant interdyestufl of thecompositionz mediate is'run into a solution of the copper com- OH v plex'from 38;8.parts of the monoazo dyestufl of the composition:

# "'oooH OH nois on N=N COOH HOzS- OH N=N SO|H Y in 400 parts of water, 400 parts of pyridine and 50 Thisdyestufl corresponds to the composition: parts of aqueous ammonia of 25% strength.

OC )u O I II=N 30.5 O Ju (i=0 i v I N=fii -so,n

Example 5 The tetrazo compound from 24.4 parts of 3,3- 9 colflclulsiqnnf the coupling, the trisazo dyedimethoxy 4,4 diammo 1,1 dipheny1 is stufl is isolated andmsubjected in substance to jected to soda-alkaline coupling in per se conconventional demethylfltmg copperingventional manner with 38.4 parts of'l-hydroxy I qdry state, the copper complex of th naphthalene 3,6,8-trisulfonic acid; The redyestufi 1s a dark powder which dissolves in water sultant intermediate is added-toasolution of 4&5= 15: as well as in concentrated sulfuric acid with a.

blue coloration, and dyes cotton in fast-marineblue shades. It corresponds to the composition;

is added in solid form to a solution of the sodium HO3S- o-gu-o 3 u -0 sozfi' v I Hols soar:

Example 7 i salt from 89 parts of the disazo dyestufi oi'vthea The diazo compound from 24.8 parts of -ni- I composition: 1 f

no. son: HO S tro-2-amino-1-methoxybenzene-4-sulfonic acid is allowed to run into a solution of the sodium salt from 82.6 parts of the disazo dyestuif-of the composition: r

in 800 parts of water, 800 parts of pyridine and 50 parts of aqueous ammonia of strength. v Upon conclusion of the coupling, the tetrakisazo in 800 partsof water, 800 parts of pyridine and dyestuif is isolated and subjected in substance to 50 parts of aqueous ammonia of 25% strength. conventional demethyl-ating coppering. Upon conclusion of the coupling, the trisazo ,dyet Ins-the dry "state, the copper complex of the stuff is isolated and subjected in substance to dedyestuff is a dark powder -which dissolves in methylating coppering. water with a. blue coloration, and dyes cotton in In the dry state, the-copper complex of the fast greenish gray shades. Itcorrespondsito the dyestuff is a dark powder which dissolves in water composition:

with a blue coloration and in concentrated sul- 5 furic acid with blue-green coloration, and dyes e f wmg table sets forth examples got adcotton in fast marine-blue shades. It correditional dyestuffs which can "be prepared in mansponds to the composition:

I ee 3 Hols -so3H'" l 110,5

a A a NO:

Examples I 4- ner entirely analogous to-theforegoing-examples The diazo compound from 30.1 parts of the from equivalent amounts of corresponding remOnOaZO dyestufi o p n? actants, whichii'are evident from the followin 0 00113 formulae which showthe' copper complex com- T pounds prepared in substance by demetlivlating 11o N=N coppering. The shade of the dyeing on cotton is,

in each case, marineblue.

HOOC C Formula oI Oopper Complex Commend Phony! nncleuel may be substituted by methyl, methoxy or carboxy,

in properties to that of Example 20.

Emu; 21 L parts of the d yestiifi obtained according the course of minutes. Boiling is continued for 15 minutes, thebaththen allowed to cool-to and the dyed materiel withdrawn-rinsed and dried. P ,1;

Example 22- The tetrezo compound from 24.4 parts of 3,3- diniethoxy 4,4 diamino-LP-diphenyl is subjected to alkaline coupling in per se conventional multant products being similar ienesm-disfliionic ecid. Theresultant interme- ---diate is min-into a, solution of the sodium salt of 50.2 ports of the copper complex compound the mono'azodyestufi corresponding to the formula i in 250 parts of pyridine, 50 parts, of aqueous ammanner with 30.4 parts of-1-hydroxynaphtlm 7:; "monia"oI'25% strengthend 500 parts or water.

515 116 v w v V V V r r component, by the copper complex compound of Upon conclusion of the coupling, the trisazo dye- ,I themonqazo dyestufi of the composition:

stufl is isolated and subjected to demethylatihiz coppering insubstance according toper-se conventional methods. v:5 In the dry state, the copper complex of the dyestufl is a dark powder which dissolves in water with a blue, in concentrated sulfuric acid with a blue-green coloration, and dyes cotton in fast" marine-blue shades. It corresponds to the'com- 10 position: i

The following table sets forth examples of adx ple 23 ditional dyestufiswhich can be prepared in man-:

ner entirely analogous toExamples 22 and 23 A Similar dy p g/ 0 he fo 20 from equivalent amounts of corresponding reactmula: I ants. which are evidentifrom the following formul-ae which show; the coppencomplex com- .S..O HE

pounds prepared in substance by demethylating coppering'. The shade of the dyeing on cotton is, in each case, marine-blue.

is obtained by replacing the copper complex compound of Example 22 serving as second coupling 17 a I 18 Having thus disclosed the invention, what is 2. The polyazo dyestufi corresponding to the claimed is: formula H038 0 ouo (I)( 7u-O g p 0 v SOZH -O( 3u (|3=O 1. A copper complex compound of a polya'zo g' lfig polyazo dyestufi miresmndmg the 4. The polyazo dyestuff corresponding to th formula a H O 5. The polyazo dyestufi corresponding to the dyestuif containing at least three and at most four sulfomc acid groups and correspondmgto m l oou-o'. OOu o. a I i l a a l i QM Hogs son-1 f HO;S o-c u o I N=-I{I S0311 the formula 6." Ihe polyazo dyestufl corresponding to the v !H)n-l OCH; OCH! N=N v (scans-1 HO S- -OH 7 7Q I b wherein :0 stands for a member selected from the formula.

H038 oou--o O--( lu O Ho,sson: Emso-ou (i=0 a N IiIONO,

group consisting of hydrogen, OH, NHz, alkyl- HANS RUCKS'IUHL. ated NI-I2, arylated NH2, acylated NH: and 803K, WALTER wEHRLL y stands for OHin ortho-position to azo, a, stands for a copperizing group selected from the 70 class consisting of COOH, OCH3, and OH, b References Cited in the file of this patent stands for a member selected from the group UNITED. STATES PATENTS consisting of hydrogen, lower alkyl, N=N I I mononuclear aryl and N02, one n is the integer Number I Name a Date 2, and each other n is one of the integers 1 and 2. 75 2,37 ,500 Sparks Feb. 27, 1945 

2. THE POLYAZO DYESTUFF CORRESPONDING TO THE FORMULA 